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Evaluation of the Giant Ferromagnetic π–d Interaction in Iron-Phthalocyanine Molecule

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Departamento de Química Física, Universidad de Sevilla, c/Profesor García González, s/n, E-41012 Sevilla, Spain
Cite this: J. Phys. Chem. A 2018, 122, 6, 1678–1690
Publication Date (Web):January 16, 2018
https://doi.org/10.1021/acs.jpca.7b11356
Copyright © 2018 American Chemical Society

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    Abstract

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    The interaction between itinerant π and localized d electrons in metal-phthalocyanines, namely, Jπd interaction, is considered as responsible for the giant negative magnetoresistance observed in several phthalocyanine-based conductors, among many other important physical properties. Despite the fundamental and technological importance of this on-site intramolecular interaction, its giant ferromagnetic nature has been only recently demonstrated by the experiments conducted by Murakawa et al. in the neutral radical [Fe(Pc)(CN)2]·2CHCl3 ( Phys. Rev. B 2015, 92, 054429). In this article, we present the theoretical evaluation of this interaction combining wave function-based electronic calculations on isolated Fe(Pc)(CN)2 molecules and density functional theory-based periodic calculations on the crystal. Our calculations confirm the ferromagnetic nature of the π–d interaction, with a coupling constant as large as Jπd/kB = 570 K, in excellent agreement with the experiments, and the presence of intermolecular antiferromagnetic interactions driven by the π–π overlap of neighboring phthalocyaninato molecules. The analysis of the wave function of the ground state of the Fe(Pc)(CN)2 molecule provides the clues of the origin of this giant ferromagnetic π–d interaction.

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    Cited By

    This article is cited by 5 publications.

    1. Barbara Brena, Biplab Sanyal, Heike C. Herper. Chemical Switching of the Magnetic Coupling in a MnPc Dimer by Means of Chemisorption and Axial Ligands. The Journal of Physical Chemistry C 2020, 124 (49) , 27185-27193. https://doi.org/10.1021/acs.jpcc.0c08448
    2. Nicolás Montenegro-Pohlhammer, Rocío Sánchez-de-Armas, Gloria Cárdenas-Jirón, Carmen J. Calzado. Elucidating the Electronic Structure and Magnetic and Conducting Properties of μ-Oxo Mn-phthalocyanine [MnPc(CN)]2O Complex. The Journal of Physical Chemistry C 2019, 123 (46) , 28359-28369. https://doi.org/10.1021/acs.jpcc.9b08046
    3. Yanhong Zhou, Xiaohong Zheng, Zi-Qiang Cheng, Ke-Qiu Chen. Current Superposition Law Realized in Molecular Devices Connected in Parallel. The Journal of Physical Chemistry C 2019, 123 (16) , 10462-10468. https://doi.org/10.1021/acs.jpcc.9b01812
    4. Ryuta Ishii, Misato Uejo, Erina Watari, Mitsuo Ikeda, Hiroshi Murakawa, Hideaki Sakai, Masaki Matsuda, Hideo Yoshioka, Masahisa Tsuchiizu, Noriaki Hanasaki. Ferrimagnetic charge order in molecular conductors with diluted localized spins exhibiting enhanced giant magnetoresistance effect. Physical Review B 2023, 108 (20) https://doi.org/10.1103/PhysRevB.108.205114
    5. Rocío Sánchez-de-Armas, Norge Cruz Hernández, Carmen J. Calzado. Copper–nitroxide based breathing crystals: a unified mechanism of gradual magnetostructural transition supported by quantum chemistry calculations. Inorganic Chemistry Frontiers 2019, 6 (5) , 1228-1237. https://doi.org/10.1039/C9QI00129H

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